Organotin sulfonates



United States Patent 1 3,095,434 ORGANOTIN SULFONATES Walter A. Stamm, Dobbs Ferry, and Arthur W. Breindel, Yonkers, N.Y., and Ashley H. Freiherg, Santa Clara, Calif., assignors to Staulfer Chemical Company, New York, N.Y., a corporation of Delaware N0 Drawing. Filed June 27, 1961, Ser. No. 119,775 10 Claims. (Cl. 260-4295) The present invention relates to certain novel organotin compounds which are useful as pesticides. The invention is particularly concerned with organotin compounds characterized by the presence of "a methylsulfonyl or mesyl (grouping (SO CH and to methods of preparing and using such entities.

The organotin compounds as contemplated herein can be formalistically depicted as follows:

wherein R signifies an alkyl group having from 1 to 12 carbon atoms such as methyl, ethyl, n-propy-l, iso-propyl, n-bu tyl, iso-butyl, sec-butyl, n-pentyLiso-pentyl, iso-hexyl, n-hexyl, n-heptyl, sec-heptyl, n-octyl, iso-octyl, iso-nonyl, n-nonyl, n-decyl, sec-decyl, iso-decyl, n-undecyl, isoindecyl, n-dodecyl, iso-dodecyl etc., an aryl nucleus such as a phenyl group or a naphthyl group in which the aryl nucleus may be substituted by relatively inert groupings such as lower alkyl, lower alkoxyl, etc.; Z designates a divalent element of group VI of the periodic table as ex emplified by oxygen and sulfur and x is an integer of from 2 to 3.

Formula I can be resolved into two sub-(generic formulae of the following configuration:

wherein Z has the values previously assigned. Structures falling within the ambit of Formula I are the dialkyltin and diaryltin bismethanesulfonates and corresponding bis-methanethiolsulfonates. sub-generic Formula Ha include the following:

Dimethylt-in bis-methanesulfonate Diet-hyltin bis-methanesulfonate Diethyltin bis-methanethiolsultonate Di-n-propyl'tin bis-methanesulfonate Di-iso-propyltin 'bis-methanesulfonate Di-n-butyltin bis-methanesulfonate Di-n-butyltin bis-methanethiolsulfonate Di-iso-butyltin bis-methanesulfonate Di-n-pentyl tin bis methanesulfona-te Di-n-hexyltin bis-methanesulfonate Di-iso-hexyltin bis-methanesulfonate Di-iso-hexyltin bis-methanethiolsulfonate Di-n-octyltin bis-methanesulfonate Di n-decylt in .bis-methanesulfonate Di-n-dodecyltin bis-methanesul fonate Dinaphlthyltin bis-methanesulfona-te Dipheny-ltin bis-methanesulfonate 18) Diphenyltin bis-methanethiolsulfonate Compounds illustrative of sub-generic Formula IIb are spelled out in the following list:

19) Tr-imethyltin methansulfonate 20) Triethyl tin methanesulfonate (21) Tri-n-propyltin methanesulfonate 22) Tri-iso-buty'ltin methanethiolsulfonate (24) Tri-iso-butyltin methanesulfonate (25) Tri-n-butyltin methanethiolsulfonate (26) Tri-n-hexyltin methanethiolsulfcnate 27) Tri-n-hexyltin methanesulfonate (28) Tri-n-heptyltin methanesulfonate Compounds illustrative of 3,095,434 Patented June 25, 1963,

The organotin compounds described herein are characterized by the presence of a methyl-sulfonyl group, i.e., a SO -CH radical. In accordance with the invention, such organotin compounds are prepared by reacting a mesyl derivative of the formula:

wherein Z has the values previously assigned and M stands for hydrogen, an ammonium radical or a metal, particularly an alkali metal such as lithium, sodium, potassium or the like with an organotin intermediate of the type represented by the following formulae:

(IVa) (R) Sn (IVb) (R) Sn'=O and (IVc) (RhAn-Cl (IVd (R) Sn-Cl wherein R has the significance as above designated. When the reaction is carried out using an org-anortin intermediate of the type as set forth in Formula IVa or IVb, the requisite mesyl derivative is desirably employed in its acid form, that is when M is hydrogen in Formula III. If, on the other hand, the reaction is performed using an organotin halide intermediate as illustrated in Formula IVc or IVd then the mesyl derivative is employed as a salt corresponding to Formula III when M is a metal or ammonium radical.

In some instances it may be advantageous to combine the reactants in the presence of a relatively inert organic solvent and in this connection, mention is made of arc-- matic hydrocarbons such as benzene, toluene, xylene etc., polyalkylene glycol ethers as represented by diethyleneglycol dimethylet-her, diethyleneglycol diethylether and the like.

As previously pointed out, the herein contemplated organotin derivatives are characterized by the presence of a methylsulfonyl function, i.e., SO -CH group.

The components utilized to provide this function are defined generally by Forrnula III which includes methanesulfonic acid, methanethiolsulfonic acid and the metal and ammonium salts thereof.

Reference is now made to the following examples which are included solely for the purpose of illustration since it will be apparent to those skilled in the art that the invention is susceptible to modifications and variations without departing from the spirit or scope thereof.

EXAMPLE 1 Di-n-Butyltin Bis-Methanesulfonate- 4 9)2 2 3)2 of a colorless, crystalline product was obtained, M.P. 306- 3 309 C., which on chemical analysis corresponded to the above structure.

EXAMPLE 2 Di-n-Propyltin Bis-Methanesulfonate (II-C3117) 2SH' 2 Tetra-n-propyltin (14.3 parts) was contacted with 9.5 parts of methanesulfonic acid under conditions identical to those of Example 1. After washing the product with hexane and cry-stallizing from methanol, 18.4 parts of a colorless crystalline solid was obtained, M.P. 279284 C. This was identified as di-n-propyltin bis-methanesulfonate.

EXAMPLE 3 Diisohexyltin Bis-Methanesulfonate (lSO-CH13 2-Sn( 2 Example 1 was repeated except that 8 parts of tetraisohexyltin was reacted with 3.3 parts of methanesulfonic acid at 140 C. for 2 hours. After crystallizing from methanol, 6.3 parts of a colorless crystalline product was obtained, M.P. 205-206" C. This was identified as diisohexyltin bis-methanesulfonate.

EXAMPLE 4 Tri-n-Propyltin M ethanesulfonate (Tl-C3117) SnOSO CI-I Tetra-n-propyltin (29.1 parts) was reacted with 9.6 parts of methanesulfonic acid for 3 hours at 95 C. under conditions similar to those of Example 1. After washing the crude material with hexane, the solid was recrystallized from benzene. Seven parts of a colorless crystalline product was obtained, M.P. 131-133 C. This was identified as tri-n-propyltin methanesulfonate.

EXAMPLE 5 Triisobutyltin Methanesulfonate (H-C4H9) 3SnO-SO2CH3 Example 1 was repeated except that 22.8 parts of tetraisobutyltin was reacted with 6.3 parts of methanesulfonic acid. The crude material was washed with hexane, and then extracted with boiling diethylether to remove a small quantity of diisobutyltin bis-methanesulfonate. After evaporating the ether, 11.5 parts of a colorless crystalline solid was obtained, M.P. 135140 C. This was identified as triisobutyltin methanesulfonate.

EXAMPLE 6 Di-n-Buty'ltin Bis-Methanesulfonate (n-C H 3SI1 2 Eighteen parts of di-n-butyltin oxide was dispersed in 200 parts of toluene. With agitation, the mixture was heated to reflux and 13.9 parts of methanesulfonic acid was added through a dropping funnel. After 3 hours of reflux, 1.3 parts of water was distilled azeotropically with toluene from the mixture and the white solid filtered off. On crystallizing from absolute ethanol, 25 parts of a colorless crystalline product was obtained, M.P. 308-310 C. This was identified as di-n-butyltin bis-methanesulfonate.

EXAMPLE 7 T riphenyltin M ethanesulfonate Tetraphenyltin (24.4 parts) was reacted with 4.8 parts of methanesulfonic acid for 4 /2 hours under conditions similar to those of Example 6. After filtering and washing twice with hot toluene, 12 parts of a colorless crystalline product was obtained, which sublimes between 275-320" C. at atmospheric pressure. This was identified as triphenyltin methanesulfonate.

EXAMPLE 8 Di-n-Butyltin Bis-Methanethiolsulfonate Twenty seven parts of sodium methanethiolsulfonate was dispersed in parts of absolute diethyleneglycol dimethylether. With agitation, this mixture was brought to C., and 30 parts of di-n-butyltin dichloride, dissolved in 20 parts of acetone, was added through a dropping funnel. After a three hour reaction time, the mixture was cooled to 80 C., and 200 parts of warm water added with continued agitation, whereupon the desired reaction product precipitated. It was filtered at room temperature, washed with water, a small amount of cold alcohol, and several times with hexane. Thirty parts of a light yellow crystalline product was obtained, M.P. 106 C. It was identified as di-n-butyltin bis-methanethiolsulfonate.

EXAMPLE 9 Tri-n-Butyltin Methanethiolsulfonate (n-C H Sn-SS O2CH3 Thirteen parts of sodium methanethiosulfonate was reacted with 33 parts of tri-n-butyltin monochloride under conditions described under Example 8. The product was a yellow oil which was separated and purified by several water washes, followed by fractional vacuum distillation. The purified tri-n-butyltin methanethiolsulfonate boiled at 98l00 C. at 0.2 mm.

EXAMPLE 10 Triphenyltin Methanethiolsulfonate A mix-ture of 13 parts of sodium methanethiolsulfonate and 38 parts of triphenyltin monochloride was refluxed with vigorous agitation in 50 parts of water and 50 parts of xylene for 6 hours. The triphenyltin methauethiolsulfonate formed between the water-xylene phases as an amorphous, colorless powder. After washing with ether and water 11 parts of purified product was obtained, M.P. 350 C.

EXAMPLE 11 T ri-lso-Decyltin M ethanesulfonate Following the procedure as given in Example 5, tetraiso-decyltin was condensed with methanesulfonic acid. The results fell in line with those of the previous examples for this type of organotin derivative.

The organotin compounds of this invention are new and useful chemical entities. For instance, they display general biocidal activity being effective in controlling insects and related pesticidal organisms. They can also be compounded or formulated to produce new and useful herbicidal compositions. Our new organotin derivatives have proved to be effective polymerization catalysts and, in this connection, mention is made of their use for producing polyurethane foams of the type formed by reacting isocyanates with glycol intermediates such as polyetherglycols. In addition to the aforesaid uses, the organotin compounds of this invention show stabilizing properties in such applications as the formulation of plastic compositions of which polyvinyl chloride and copolymers thereof are examples.

It has previously been pointed out that the herein contemplated organotin compounds exhibit insecticidal activity and this valuable property has been utilized in formulating insecticidal compositions containing the aforesaid entities as an active component therein. It has also been discovered that the organotin derivatives of the invention exhibit activity toward a variety of microorganisms such as fungi and the like and this represents 6. Tri-iso-butyltin methanesulfonate. another new and valuable utility for these materials. 7. Tri-iso-hexyltin methanesul-fonate.

We claim: 8. Di-n-butyltin bis-methanethiolsulfonate.

1. An organotin compound of the formula: V 9. T ri-n-butyltin methanethiolsulfonate.

(R)XSH (Z SO'2 CH3)4 X 5 10. Triphenyltin methanethiolsulfonate.

wherein R is selected from the class consisting of an References Cited in the file of this patent alkyl group of from 1 to 12 carbon atoms, a phenyl UNITED STATES PATENTS group and a naphthyl group, Z is selected from the class consisting of oxygen and sulfur atoms and x designates 10 2,910,452 Crauland 1959 an integer of from 2 to 3. OTHER REFERENCES Di'n'propyltm bwmethanesulfonatfl Luijten: Investigations in Org. Chem. (October 3. Tri-n-prop-yltin methanesulfonate. 1955) h Pu 1s ed by Tm Research (Mlddlesex, England), 4. Dl-n-butyltm bis-methanesulfonate. ml 9, 15, 22 and 24 5. Tri-n-butyltin methanesulfonate. 

1. AN ORGANOTIN COMPOUND OF THE FORMULA: 